JP6620694B2 - Release film - Google Patents

Description

  The present invention relates to a film having excellent peelability. In particular, the present invention relates to a peeling film or the like used in a manufacturing process of an electronic component or an electronic substrate or a manufacturing process of a thermosetting resin member such as a fiber reinforced plastic. More specifically, the present invention relates to a peelable film that is particularly useful as a release film, a release liner, a carrier for producing a composite material, a separator film for a protective material, or the like.

  Polypropylene films are excellent in light weight, thermal stability and mechanical properties, and are widely used as industrial material films including packaging. Particularly in recent years, it has been used as a non-silicone mold release material in the manufacturing process of electronic parts, electronic substrates, and the manufacturing process of thermosetting resin members such as fiber reinforced plastics, etc. by utilizing the low surface energy of polypropylene film. Widely used in protective materials and mold release materials.

  As such a polypropylene film, for example, a film containing a polypropylene resin and an amorphous α-olefin copolymer elastomer has been proposed (Patent Document 1).

JP 2010-184990 A

  However, the film described in Patent Document 1 has insufficient peelability (at low speed peel). In addition, in recent years, we have examined release films, release liners or separator films for use in surface protection films and adhesive tapes in the manufacturing process of electronic components or electronic substrates, and films for use as carriers in the production of composite materials. In doing so, the use application of peeling the film at a high speed (for example, 1000 mm / min or more, 3000 mm / min or more, 5000 mm / min or more, 10000 mm / min or more, etc.) is regarded as important. This usage is because of a request to increase the processing speed (that is, a request to improve productivity). In such a use application called high-speed peeling, light peelability is important. However, in the film of Patent Document 1, the peeling force when peeling at the above-described high speed is too high, so that the film is wrinkled or broken. The present inventors have found that there is a problem.

  Therefore, there is still a need for a film that has good peelability when peeled at a low speed and also has good peelability when peeled at a high speed.

  An object of the present invention is to provide a film that has good peelability when peeled at a low speed and also has good peelability when peeled at a high speed.

In order to solve the above-mentioned problems, the present inventors have studied in detail about the peelable film. As a result, when the specific gravity of the resin component, which is the main component of the outermost layer of the film, and the glass transition temperature are combined in a specific range, the above problems are solved and the present invention is completed. It was. The present invention includes the following aspects.
Item 1.
At least a peelable film in which a base material layer and an outermost layer are laminated in order,
The outermost layer contains a resin component as a main component,
The resin component has a specific gravity of 1.15 g · cm ⁻³ or less,
The glass transition temperature of the resin component is −10 to 75 ° C.,
A peelable film characterized by that.
Item 2.
Item 2. The peelable film according to Item 1, wherein an intermediate layer is formed between the base material layer and the outermost layer.
Item 3.
Item 3. The peelable film according to Item 2, wherein the intermediate layer contains at least one selected from the group consisting of a polyolefin resin B1 having a carboxyl group and a polyolefin resin B2 having a hydroxyl group.
Item 4.
Item 4. The peelable film according to Item 3, wherein the polyolefin resin B1 is a polyolefin obtained by graft copolymerization of maleic acid and / or maleic anhydride.
Item 5.
Item 5. The peelable film according to Item 3 or 4, wherein the polyolefin resin B2 is a polyolefin obtained by graft copolymerization of a hydroxyl group-containing (meth) acrylic acid ester and / or a hydroxyl group-containing vinyl ether.
Item 6.
The peelable film according to any one of Items 1 to 5, wherein the resin component contained as a main component of the outermost layer includes a structural unit derived from 4-methylpentene-1.
Item 7.
Item 7. The peelable film according to any one of Items 1 to 6, wherein the resin component contained as a main component of the outermost layer includes a 4-methylpentene-1 polymer A.
Item 8.
The resin component contained as a main component of the outermost layer includes (1) a 4-methylpentene-1 polymer A and (2) an olefin resin A ′ other than the 4-methylpentene-1 polymer A. The peelable film according to any one of Items 1 to 7, which comprises:
Item 9.
The peelable film according to any one of Items 1 to 8, wherein a T-peel peeling force (1000 mm / min) to the polyester adhesive tape on the film surface on the outermost layer side is 0.1 to 1.0 N / 25 mm. .
Item 10.
The said polymer A is a peelable film in any one of said claim | item 7-9 which has melting | fusing point of the range of 80 to 240 degreeC.
Item 11.
Item 11. The peelable film according to any one of Items 1 to 10, wherein the outermost layer has a thickness of 0.1 to 3.0 µm.
Item 12.
Item 12. The peelable film according to any one of Items 2 to 11, wherein the intermediate layer has a thickness of 0.04 to 1.5 µm.
Item 13.
The peelable film according to any one of Items 1 to 12, wherein a protruding peak height (Rpk) in a load curve obtained from a roughness curve of the film surface on the outermost layer side is 0.005 to 0.04 μm. .
Item 14.
14. The peelable film according to any one of Items 1 to 13, which is used for applications having a peel rate of 1000 m / min or more.

  The peelable film of the present invention has good peelability when peeled at a low speed and also has good peelability when peeled at a high speed. Therefore, in particular, it is suitably used as a release film or the like used in a manufacturing process of an electronic component or an electronic substrate or a manufacturing process of a thermosetting resin member such as a fiber reinforced plastic. In particular, it can be suitably used as a release film, a release liner or a separator film for use in a surface protection film, an adhesive tape, etc. in the production process of an electronic component or an electronic substrate, and a carrier for producing a composite material.

It is sectional drawing which shows the peelable film in Example 1 typically.

Releasable film The present invention is a peelable film in which at least a base material layer and an outermost layer are laminated in order,
The outermost layer contains a resin component as a main component,
The resin component has a specific gravity of 1.15 g · cm ⁻³ or less,
The glass transition temperature of the resin component is −10 to 75 ° C.,
The present invention relates to a peelable film.
The peelable film of the present invention is a film in which at least a base material layer and an outermost layer are laminated in order. For example, an intermediate layer described later may be formed between the base material layer and the outermost layer.
In the present invention and the present specification, the “main component” means a component having the highest content in all the components contained in the target layer, and all the components contained in the target layer include On the other hand, it is preferably a component occupying 50% by mass or more, more preferably a component occupying 70% by mass or more, further preferably a component occupying 90% by mass or more, and even more preferably 95% by mass or more. It is a component, particularly preferably a component occupying 98% by mass or more, and most preferably a component occupying 99% by mass or more.

Base material layer The peelable film of the present invention has a base material layer. The material of the base material layer is not particularly limited, but it is preferable that the resin component is a main component.

  Examples of the resin component that is the main component of the base material layer include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polypropylene naphthalate, polytrimethylene terephthalate, polybutylene terephthalate, and other polyester resins, polyethylene, polypropylene, and the like. Polyolefin resin, polystyrene resin, acetyl cellulose resin such as triacetyl cellulose, acrylic resin such as polymethyl methacrylate, polyurethane resin, polycarbonate resin, polyamide resin, polyvinyl chloride resin, etc. . A base material layer may contain only 1 type of the said resin, and may contain it in combination of 2 or more type. The base material layer in the peelable film of the present invention may be a layer containing a resin selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polypropylene, and polystyrene from the viewpoint of processing suitability of the intermediate layer and the outermost layer. From the viewpoint of heat resistance, a layer containing a polyethylene terephthalate resin is more preferable.

  The base material layer may be a layer formed from any of an unstretched film, a uniaxially stretched film, or a biaxially stretched film. From the viewpoint of processing suitability, transparency and dimensional stability, the base material layer is preferably a biaxially stretched film.

  The thickness of the base material layer is preferably 15 μm or more, more preferably 20 μm or more, from the viewpoint of processing suitability. The thickness of the base material layer is preferably 125 μm or less, more preferably 50 μm or less, from the viewpoint of handling properties when using the product. The thickness of the base material layer is measured according to JIS C-2151 using a micrometer (JIS B-7502).

  When the peelable film of the present invention includes an intermediate layer, a surface treatment may be applied to one or both sides of the base material layer as desired for the purpose of improving the adhesion between the base material layer and the intermediate layer described later. Examples of the surface treatment include surface roughening treatment such as sand blast treatment and solvent treatment, corona discharge treatment, plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.

Intermediate layer The peelable film of the present invention may have an intermediate layer formed on at least one surface of the base material layer. More preferably, in the peelable film of the present invention, an intermediate layer may be formed between the base material layer and the outermost layer. An intermediate | middle layer can raise the adhesiveness of a base material layer and the outermost layer mentioned later, for example, and can raise the intensity | strength of a film.

  When the peelable film of the present invention has an intermediate layer, the intermediate layer preferably contains at least one selected from the group consisting of a polyolefin resin B1 having a carboxyl group and a polyolefin resin B2 having a hydroxyl group.

The polyolefin resin B1 having a carboxyl group preferably has an acid value of 10 to 100 mgKOH / g, more preferably 30 to 80 mgKOH, and still more preferably 40 to 60 mgKOH, from the viewpoint of adhesion between the base material layer and the outermost layer. The acid value here is a value measured by a method based on JIS0070 (neutralization titration method).
The polyolefin resin B2 having a hydroxyl group preferably has a hydroxyl value of 10 to 100 mgKOH / g, more preferably 30 to 80 mgKOH, and still more preferably 40 to 60 mgKOH, from the viewpoint of adhesion between the base material layer and the outermost layer. The hydroxyl value here is a value measured by a method based on JIS0070 (neutralization titration method).

  The polyolefin resin B1 having a carboxyl group and the polyolefin resin B2 having a hydroxyl group can be produced, for example, by introducing a carboxyl group or a hydroxyl group into the polyolefin resin.

  As the polyolefin resin, a homopolymer of at least one monomer selected from the group consisting of ethylene and olefins having 3 to 20 carbon atoms, or a copolymer of two or more monomers selected from these, ethylene and Examples thereof include a copolymer of at least one monomer selected from the group consisting of olefins having 3 to 20 carbon atoms and another polymerizable monomer. Examples of the olefin include α-olefins and diolefins such as butadiene. Examples of the polyolefin resin include polyethylene such as high density polyethylene, low density polyethylene, and linear low density polyethylene resin, polypropylene, polyisobutylene, poly (1-butene), poly-4-methylpentene, polyvinylcyclohexane, polystyrene, poly (P-methylstyrene), poly (α-methylstyrene), ethylene / propylene block copolymer, ethylene / propylene random copolymer, propylene / 1-butene block copolymer, propylene / 1-butene random copolymer , Ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methyl methacrylate copolymer, ethylene / vinyl acetate / methyl methacrylate, styrene / butadiene / styrene copolymer, ionomer resin and the like. .

  The polyolefin resin is composed of propylene, ethylene, and 4 to 20 carbon atoms (preferably 4 to 12 carbon atoms) from the viewpoint of solubility in a solvent when obtaining a coating liquid and film formability when obtaining a coating film. A copolymer with at least one monomer selected from the group consisting of α-olefins is preferred. Here, specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, and the like. It is done. In this embodiment, the polyolefin resin may be a copolymer of propylene and one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms, or propylene, ethylene and It may be a copolymer with two or more monomers selected from the group consisting of α-olefins having 4 to 20 carbon atoms. The polyolefin resin is more preferably a resin obtained by copolymerizing at least propylene and ethylene or 1-butene from the viewpoint of solubility in a solvent when obtaining a coating liquid.

In one embodiment of the present invention, the polyolefin resin is preferably a resin obtained by copolymerizing at least propylene and ethylene. In this embodiment, the content of the structural unit derived from propylene in the polyolefin resin is preferably 50 to 75 mol%, more preferably 60 to 70 mol%, based on all the structural units constituting the polyolefin resin. . Further, the content of the structural unit derived from ethylene in the polyolefin resin is preferably 25 to 50 mol%, more preferably 30 to 40 mol% based on all the structural units constituting the polyolefin resin. The polyolefin resin may contain a constituent unit derived from an α-olefin and / or other polymerizable monomer other than the constituent unit derived from propylene and ethylene, and the content thereof is all the constituent units constituting the polyolefin resin. Is preferably 40 mol% or less, and more preferably 30 mol% or less.
In this embodiment, the degree of crystallinity measured by X-ray diffraction of the polyolefin resin is preferably 2 to 20% from the viewpoint of solubility in a solvent and a film formability as a coating film when obtaining a coating liquid. Yes, more preferably 5 to 18%.
In this embodiment, the polyolefin resin may be a block copolymer or a random copolymer, but is soluble in a solvent when obtaining a coating solution and film formability when obtaining a coating film. From this viewpoint, a random copolymer is preferable.

  In another embodiment of the present invention, the polyolefin resin is preferably a resin obtained by copolymerizing at least propylene and 1-butene. In this embodiment, the content of the structural unit derived from propylene in the polyolefin resin is preferably 50 to 95 mol%, more preferably 60 to 93 mol%, based on all the structural units constituting the polyolefin resin. More preferably, it is 70-90 mol%. Further, the content of the structural unit derived from 1-butene in the polyolefin resin is preferably 5 to 50 mol%, more preferably 7 to 40 mol% based on all the structural units constituting the polyolefin resin. More preferably, it is 10-30 mol%. In addition to the structural units derived from propylene and 1-butene, the polyolefin resin may contain structural units derived from ethylene, other α-olefins and / or other polymerizable monomers. Preferably it is 10 mol% or less based on all the structural units which comprise resin, More preferably, it is 5 mol% or less.

In one embodiment of the present invention in which the polyolefin resin is a resin obtained by copolymerizing at least propylene and 1-butene, the intrinsic viscosity [η] of the polyolefin resin is preferably 0.1 to 12 dl / g, more preferably 0.00. 5-12 dl / g, more preferably 1-12 dl / g. It is preferable for the intrinsic viscosity [η] of the polyolefin resin to be in the above range since the coating suitability of the coating liquid and the film formability of the coating film are good.
Here, the intrinsic viscosity [η] is measured at 135 ° C. using decalin as a solvent. Specifically, about 20 mg of the copolymer is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution and diluting, the specific viscosity ηsp is measured in the same manner, and the value of ηsp / C can be obtained as the limiting viscosity by extrapolating the concentration (C) to 0. .

  In this embodiment, the molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) of the polyolefin resin is preferably 3 or less, more preferably 2.0 to 3.0, and even more preferably 2.0 to 2. .5. It is preferable for the molecular weight distribution (Mw / Mn) of the polyolefin resin to be in the above range since the film formability of the coating film and the stability of the coating liquid are good. The molecular weight distribution (Mw / Mn) is calculated as the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) method. The GPC apparatus used in the GPC method is not particularly limited, and is a commercially available high-temperature GPC measuring instrument capable of analyzing the molecular weight of polyolefins, for example, a high-temperature GPC measuring instrument with a built-in differential refractometer (RI) manufactured by Tosoh Corporation. HLC-8121GPCHT or the like can be used. In this case, for example, a GPC column manufactured by Tosoh Corporation and three connected TSKgelGMHHR-H (20) HT is used, the column temperature is set to 140 ° C., trichlorobenzene is used as an eluent, Measured at 1.0 ml / min. Usually, a calibration curve is prepared using standard polystyrene, and a weight average molecular weight (Mw) and a number average molecular weight (Mn) are obtained by polystyrene conversion.

In this embodiment, the melting point (T _m ) of the polyolefin resin measured by differential scanning calorimetry (DSC) is preferably 60 to 140 ° C., more preferably 70 to 130 ° C. When the melting point T _m of a polyolefin resin is within the above range is preferable because film forming property of the coating film is good. The melting point _Tm was determined by using a differential scanning calorimeter (for example, Perkin Elmer Co., Ltd., input compensation type DSCDiamond DSC), packing about 2 mg of sample in an aluminum sample holder, and increasing the temperature from 0 ° C. to 280 ° C. under a nitrogen flow. The temperature is increased at a rate of ℃ / min, held at 280 ° C for 5 minutes, then the temperature is decreased to 30 ° C at 10 ° C / min, and the endothermic peak is obtained when the temperature is increased again to 280 ° C at 10 ° C / min. Can do.

  In this embodiment, the polyolefin resin may be a block copolymer or a random copolymer, but the solubility in a solvent when obtaining a coating liquid and the film-forming property when obtaining a coating film. From the viewpoint, a random copolymer is preferable.

  The polyolefin resin B1 having a carboxyl group can be produced, for example, by introducing a carboxyl group into the polyolefin resin. Introduction of a carboxyl group can be obtained, for example, by graft copolymerizing a polyolefin resin and at least one monomer selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, and derivatives thereof. These monomers can be used alone or in combination of two or more for copolymerization with a polyolefin resin. The monomer is preferably graft copolymerized in an amount of 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin to be graft copolymerized. Here, it is preferable that the amount of the monomer is equal to or more than the above lower limit because it is easy to improve the adhesion of the intermediate layer to the base layer and the outermost layer described later, and the amount of the monomer is equal to or more than the above lower limit. Since brittleness does not increase and cohesive peeling hardly occurs, it is preferable.

  Examples of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and derivatives thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and fumaric acid, anhydrides of the unsaturated carboxylic acids, and unsaturated carboxylic acids. Examples include acids and derivatives of the unsaturated carboxylic anhydrides (eg, acid halides, amides, imides, esters, etc.). Specific examples include maleic anhydride, itaconic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, and diethyl citraconic acid. The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, and derivatives thereof are preferably maleic acid and / or maleic anhydride from the viewpoint of ease of production.

  As a method for introducing a carboxyl group into a polyolefin resin, for example, a polyolefin resin solution obtained by dissolving a polyolefin resin in an organic solvent is selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and derivatives thereof. A method in which at least one monomer and a radical polymerization initiator are added and heated and stirred to cause graft copolymerization, and a melt obtained by heating and melting a polyolefin resin is mixed with an unsaturated carboxylic acid or an unsaturated carboxylic acid. A method of adding at least one monomer selected from the group consisting of anhydrides and derivatives thereof and a radical polymerization initiator, stirring and graft copolymerizing, polyolefin resin, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride At least one monomer selected from the group consisting of products and derivatives thereof; A method of supplying a mixture obtained by pre-mixing with a radical polymerization initiator to an extruder and performing a graft copolymerization reaction while heating and kneading, from the group consisting of unsaturated carboxylic acid, unsaturated carboxylic acid anhydride and derivatives thereof After impregnating a polyolefin resin with a solution obtained by dissolving at least one selected monomer and a radical polymerization initiator in an organic solvent, the mixture is heated to the highest temperature at which the polyolefin resin does not dissolve, and graft copolymerization reaction is performed. And the like.

  The radical polymerization initiator used is not particularly limited as long as it initiates polymerization of the polyolefin resin and the monomer, and examples thereof include organic peroxides, organic peresters, and azo compounds. The radical polymerization initiator is preferably an organic peroxide or an organic perester. Examples of the organic peroxide include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis ( tert-butylperoxyisopropyl) benzene, lauroyl peroxide and the like. Organic peresters include tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butyl peroxide) Hexane, tert-butyl benzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, tert-butyl perdiethyl acetate, etc. Is mentioned.

  The radical polymerization initiator is dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di ( Dialkyl peroxides such as tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are more preferable from the viewpoint of ease of production.

  The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin to be graft copolymerized from the viewpoint of ease of production.

  The polyolefin resin B1 having a carboxyl group is preferably a polyolefin obtained by graft copolymerization with at least one monomer selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and derivatives thereof, and more preferably. Is a polyolefin obtained by graft copolymerization of maleic acid and / or maleic anhydride.

  The polyolefin resin B2 having a hydroxyl group can be produced, for example, by introducing a hydroxyl group into the polyolefin resin. Introduction of a hydroxyl group can be obtained, for example, by graft copolymerizing the polyolefin resin and at least one monomer selected from the group consisting of a hydroxyl group-containing (meth) acrylic acid ester and a hydroxyl group-containing vinyl ether. These monomers can be used alone or in combination of two or more for copolymerization with the polyolefin resin. The monomer is preferably graft copolymerized so as to be 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin to be graft copolymerized. Here, it is preferable that the amount of the monomer is not less than the above lower limit because the adhesion of the intermediate layer to the base layer and the outermost layer described later is easy to increase, and if the amount of the monomer is not less than the above lower limit, the brittleness of the intermediate layer is preferable. This is preferable because aggregation does not occur without increasing.

Examples of the hydroxyl group-containing (meth) acrylic acid ester include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate, and (meth) acrylic. Examples include acid polyethylene glycol and (meth) acrylic acid polypropylene glycol. The hydroxyl group-containing (meth) acrylic acid ester monomer is preferably hydroxyethyl (meth) acrylate from the viewpoint of ease of production.
Examples of the hydroxyl group-containing vinyl ether include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether and the like. The hydroxyl group-containing vinyl ether is preferably 2-hydroxyethyl vinyl ether from the viewpoint of ease of production and film formability of the coating film.

  The polyolefin resin B2 having a hydroxyl group is preferably a polyolefin obtained by graft copolymerization of a hydroxyl group-containing (meth) acrylic acid ester and / or a hydroxyl group-containing vinyl ether.

  At least one resin component selected from the group consisting of a polyolefin resin B1 having a carboxyl group and a polyolefin resin B2 having a hydroxyl group may contain a structural unit derived from styrene. When the resin component contains a structural unit derived from styrene, the introduction method includes, for example, copolymerizing with styrene as a monomer component together with a polyolefin resin.

  The weight average molecular weight (Mw) of the polyolefin resin B1 having a carboxyl group and the polyolefin resin B2 having a hydroxyl group is 1000 from the viewpoint of easily achieving both the solubility in a solvent and the film-forming property of a coating film when obtaining a coating liquid. It is preferably ˜200000, more preferably 1000 to 50000. The weight average molecular weight (Mw) is measured in the same manner as the method for measuring the molecular weight distribution (Mw / Mn) described above.

  The glass transition temperature (Tg) of the polyolefin resin B1 having a carboxyl group and the polyolefin resin B2 having a hydroxyl group is preferably −5 to 60 ° C., and preferably 0 to 50 ° C. from the viewpoint of the film formability of the coating film. It is more preferable. The glass transition temperature can be measured according to JIS7121.

  The intermediate layer includes, for example, a coating solution containing at least one selected from the group consisting of a polyolefin resin B1 having a carboxyl group and a polyolefin resin B2 having a hydroxyl group, and at least one solvent. It is formed by coating on one surface and removing the solvent from the resulting coating layer.

  The solvent is not particularly limited as long as the polyolefin resin B1 or B2 can be dissolved. Examples of the solvent include organic solvents such as aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as n-heptane and methylcyclohexane. Can be mentioned. The boiling point of the solvent is preferably 10 to 150 ° C., more preferably 20 to 120 ° C., from the viewpoint of easily improving the handling properties of the coating liquid and the production efficiency of the peelable film.

  The concentration of the polyolefin resin B1 or B2 in the coating liquid is preferably 1 to 15% by mass based on the total amount of the coating liquid from the viewpoint of the stability of the coating liquid and the coating suitability, and 2 to 5 More preferably, it is mass%. A coating method is not specifically limited, A conventionally well-known coating method can be used suitably. Examples of the coating method include a method using a blade coater, air knife coater, roll coater, bar coater, gravure coater, micro gravure coater, rod blade coater, lip coater, die coater, curtain coater, printing machine and the like.

  The method for removing the solvent from the coating layer is not particularly limited as long as the solvent can be volatilized. Note that removing the solvent does not mean that the solvent is completely removed, but also includes removing the solvent to such an extent that a layer is formed. Examples of the method for removing the solvent include a method in which the coating layer is left to dry and a method in which drying is performed by heating. It is preferable to dry at 90-110 degreeC from a viewpoint with which solvent removal and base-material deformation prevention are compatible, and it is more preferable to dry at 95-105 degreeC.

  The thickness of the intermediate layer is preferably 0.04 μm or more, more preferably 0.1 μm or more, from the viewpoint of easily achieving both film formability and adhesion. The thickness of the intermediate layer is preferably 1.5 μm or less, more preferably 0.5 μm or less, from the viewpoint of the coating suitability of the outermost layer. The thickness of the intermediate layer is measured by a light interference method using a surface / layer cross-sectional shape measuring instrument (for example, “VertScan (registered trademark) 2.0” manufactured by Ryoka Systems Inc.).

Outermost layer The peelable film of the present invention has an outermost layer formed on the base material layer. The outermost layer is a layer for imparting peelability to the peelable film of the present invention, and is a layer containing a resin component as a main component. Here, the main component means a component having the largest content in the outermost layer. The content of the resin component in the outermost layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and 95% by mass with respect to all components contained in the outermost layer. % Or more is more preferable, 98 mass% or more is especially preferable, and 99 mass% or more is the most preferable. The upper limit of the content of the resin component in the outermost layer is 100% by mass. As will be described later, the outermost layer may contain components other than the resin component (for example, additives).

The specific gravity of the resin component that is the main component of the outermost layer is 1.15 g · cm ⁻³ or less. If the specific gravity of the resin component, which is the main component of the outermost layer of the peelable film of the present invention, exceeds 1.15 g · cm ⁻³ , the peeling force of the film is too strong, and the film causes wrinkles and breaks. There is a risk of adversely affecting tangible objects (for example, electronic components) on the side to be used. Wherein the upper limit value of the specific gravity of the resin component which is the outermost layer of the main component is preferably 1.0 g · ^{cm -3} or less, more preferably 0.95 g · ^{cm -3} or less, 0.9 g · ^{cm -3} or less More preferred is 0.85 g · cm ⁻³ or less.
The lower limit of the specific gravity of the resin component that is the main component of the outermost layer is preferably at least 0.5 g · cm ⁻³ or more, more preferably 0.6 g · cm ⁻³ or more, and 0.7 g · cm ⁻³ or more. Is more preferable, and 0.8 g · cm ⁻³ or more is particularly preferable. When the specific gravity of the resin component that is the main component of the outermost layer of the peelable film of the present invention is less than 0.5 g · cm ⁻³ , the resin that is the main component of the outermost layer aggregates before peeling off from the tangible object to be stuck. There is a risk of destruction.
In addition, when the said resin component is a 2 type, or 3 or more types of resin component, the said specific gravity points out the specific gravity of the said 2 types, or 3 or more types of resin component whole.

The glass transition temperature of the resin component which is the main component of the outermost layer is −10 to 75 ° C. When the glass transition temperature of the resin component that is the main component of the outermost layer of the peelable film of the present invention is lower than −10 ° C. When peeling from a tangible object at a high speed, there is a risk that the peeling force will not decrease. In addition, when the glass transition temperature of the resin component exceeds 75 ° C., the peeling force of the film is too strong, and thus the tangible object (for example, electronic component) on the side to be pasted that causes wrinkles or breaks in the film There is a risk of adverse effects.
In addition, when the said resin component is 2 types, or 3 or more types of resin components, the said glass transition temperature points out the glass transition temperature of the said 2 types, or 3 or more types of resin component whole.

The resin component in the outermost layer is not particularly limited, but is a structural unit derived from 4-methylpentene-1 (4-methyl-1-pentene) (hereinafter, a structural unit derived from 4-methylpentene-1). It is preferable to include. In this specification, a structural unit may be called a structural part, a structural unit, or a structural part. The content of the structural unit is not limited. Hereinafter, the case where the outermost resin component includes a structural unit derived from 4-methylpentene-1 will be described as a preferred example, but the outermost resin component includes a structural unit derived from 4-methylpentene-1. Even if not, the effect of the present invention is exhibited when the specific gravity and glass transition temperature of the resin component satisfy the specific gravity and glass transition temperature defined in the present invention, respectively.
1 mass% or more is preferable, 5 mass% or more is more preferable, 10 mass% or more is further more preferable, and the lower limit of content of the structural unit derived from 4-methylpentene-1 with respect to a resin component is 15 mass% or more. Particularly preferable is 20% by mass or more, and most preferable is 25% by mass or more. Moreover, 99 mass% or less is preferable, as for the upper limit of content of the structural unit derived from 4-methylpentene-1 with respect to a resin component, 95 mass% or less is more preferable, 90 mass% or less is more preferable, 85 mass% The following is particularly preferable, 80% by mass or less is particularly preferable, and 75% by mass or less is most preferable.
Further, the lower limit of the content of the structural unit derived from 4-methylpentene-1 with respect to all components in the outermost layer is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. 15% by mass or more is particularly preferable, 20% by mass or more is particularly preferable, and 25% by mass or more is most preferable. Moreover, 99 mass% or less is preferable, as for the upper limit of content of the structural unit derived from 4-methylpentene-1 with respect to all the components in the outermost layer, 95 mass% or less is more preferable, and 90 mass% or less is more preferable. , 85% by mass or less is particularly preferable, 80% by mass or less is particularly preferable, and 75% by mass or less is most preferable.
When the content of the structural unit derived from 4-methyl-1-pentene in the resin component or in the outermost layer is equal to or higher than the lower limit of the above range, the peelability is further improved, and is preferably equal to or lower than the upper limit. This is preferable because the solubility in a solvent for obtaining a coating liquid is further improved.

The resin component constituting the outermost layer includes, in one aspect, a 4-methylpentene-1 polymer A, and in another aspect, the 4-methylpentene-1 polymer A and (2) the 4-methyl An olefin resin A ′ other than the pentene-1 polymer A is included. More specifically, when the resin component constituting the outermost layer is (I) the resin component is 4-methylpentene-1 polymer A, (II) the resin component is (1) 4-methylpentene-1 When the olefin resin A ′ other than the polymer A and (2) the 4-methylpentene-1 polymer A, (III) the resin component is (1) the 4-methylpentene-1 polymer A, And (3) When the thermoplastic resin component is different from the resin components (1) and (2), (IV) When the resin component is (1), (2) and (3) , Etc. That is, with respect to the resin component constituting the outermost layer, any of the above cases (I) to (IV) is an embodiment included in the present invention, and in any of the above cases (I) to (IV), The specific gravity of the resin component is 1.15 g · cm ⁻³ or less, and the glass transition temperature of the resin component is −10 to 75 ° C.

  The case where the resin component is 4-methylpentene-1 polymer A (in the case of (I) above) will be described. The 4-methylpentene-1 polymer is a polymer containing a structural unit derived from 4-methylpentene-1, and is a 4-methylpentene-1 homopolymer or a copolymer of 4-methylpentene-1. is there. The resin component may contain one kind of 4-methylpentene-1 series polymer as a 4-methylpentene-1 series polymer, or a combination of two or more kinds of 4-methylpentene-1 series polymers. You may contain.

  The copolymer of 4-methylpentene-1 is, for example, at least one selected from the group consisting of 4-methylpentene-1 and an α-olefin having 2 to 20 carbon atoms excluding 4-methylpentene-1. Examples include copolymers with seed olefins. Moreover, in addition to the structural unit derived from 4-methylpentene-1 and the structural unit derived from the olefin, a structural unit derived from another polymerizable monomer may be contained. Examples of other polymerizable monomers include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane, vinyl esters such as vinyl acetate, unsaturated organic acids such as maleic anhydride or derivatives thereof, butadiene, and the like. Conjugated dienes such as isoprene, pentadiene, 2,3-dimethylbutadiene, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7 -Methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene- 2-norbornene, 6- Non-conjugated polyenes such as olomethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene Etc. When the copolymer contains a structural unit derived from another polymerizable monomer, the content of the structural unit is determined in the copolymer A from the viewpoint of solubility in a solvent when obtaining a coating liquid. The total structural unit is 100 mol%, preferably 5 mol% or less, more preferably 3 mol% or less. The at least one olefin selected from the group consisting of α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1 is preferably an α-olefin having 2 to 4 carbon atoms (ie, ethylene and carbon). At least one olefin selected from the group consisting of an α-olefin having 3 to 4 atoms, more preferably propylene and 1-butene. The copolymer of 4-methylpentene-1 may be a copolymer containing one olefin selected from the group consisting of α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1. It may be a copolymer containing two or more olefins. That is, the copolymer of 4-methylpentene-1 may be a binary copolymer, a ternary copolymer, or a quaternary or higher copolymer.

  Although the lower limit of the ratio of the structural unit derived from 4-methylpentene-1 to the copolymer of 4-methylpentene-1 is not particularly limited, for example, 1% by mass or more is preferable, and 5% by mass or more is more preferable. 10 mass% or more is further more preferable, 15 mass% or more is especially preferable, 18 mass% or more is especially preferable, and 25 mass% or more is the most preferable. The upper limit of the proportion of the structural units is, for example, preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, particularly preferably 85% by mass or less, and particularly preferably 82% by mass or less. Preferably, 75 mass% or less is the most preferable. The ratio is preferably increased from the viewpoint of easy development of the film releasability, and is preferably decreased from the viewpoint of film moldability and molding temperature.

  The proportion of structural units derived from at least one olefin selected from the group consisting of α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1 in the copolymer of 4-methylpentene-1 is From the viewpoint of film moldability and molding temperature, it is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass based on the total structural units constituting the 4-methylpentene-1-based polymer. % Or less, more preferably 85% by mass or less, particularly preferably 82% by mass or less, and most preferably 75% by mass or less. The proportion is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass from the viewpoint that the release property of the film is easily expressed by the 4-methylpentene-1 polymer. More preferably, it is 15% by mass or more, particularly preferably 18% by mass or more, and most preferably 25% by mass or more.

Here, the structural unit derived from 4-methylpentene-1 in the 4-methylpentene-1 series polymer, from the group consisting of α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1. Content of the structural unit derived from the at least 1 sort (s) of selected olefin, the structural unit derived from another polymerizable monomer, etc. can be measured by ¹³ CNMR, for example. Specifically, using a nuclear magnetic resonance apparatus (for example, high temperature Fourier transform nuclear magnetic resonance apparatus (high temperature FT-NMR), JNM-ECP500, etc., manufactured by JEOL Ltd.), solvent: orthodichlorobenzene / heavy benzene (80 / 20 volume%) mixed solvent, sample (polymer A) concentration: 55 mg / 0.6 mL, measurement temperature: 135 ° C., observation nucleus: ¹³ C (125 MHz), sequence: single pulse proton decoupling, pulse width: 4. 27.50 ppm can be measured as a reference value for chemical shift under the conditions of 7 μs (45 ° pulse), repetition time: 5.5 seconds, and number of integrations of 10,000 times or more.

  Although the melting point of the 4-methylpentene-1 polymer is not limited, it is preferably 80 to 240 ° C., more preferably 90 to 200 ° C., still more preferably 100 to 190 ° C., from the viewpoint of film moldability and molding temperature. Especially preferably, it is 120-140 degreeC. The melting point can be measured using a DSC measuring device (for example, an input compensation DSC Diamond DSC manufactured by Perkin Elmer). Specifically, using a sample as described in the examples, the temperature was raised from 0 ° C. to 280 ° C. at a rate of 10 ° C./minute, held at 280 ° C. for 5 minutes, and then 10 ° C./minute to 30 ° C. After cooling, it can be measured as an endothermic peak when the temperature is increased again to 280 ° C. at 10 ° C./min. The melting point of the 4-methylpentene-1 polymer can be adjusted to the above range by adjusting the type and composition ratio of the monomer constituting the 4-methylpentene-1 polymer and the regularity of the polymer. it can.

  The melt flow rate (MFR) of the 4-methylpentene-1 polymer is not limited, but is preferably 0.1 to 200 g / 10 minutes, more preferably 1 to 150 g / 10 minutes, from the viewpoint of moldability of the film. More preferably, it is 2 to 25 g / 10 min, particularly preferably 3 to 20 g / 10 min, and most preferably 5 to 15 g / 10 min. According to JIS K7210, the MFR is a 4-methylpentene-1 polymer having a melting point of 220 ° C. or higher, a measurement condition of a temperature of 260 ° C. and a load of 49.03 N, and a 4-methylpentene-1 polymer having a melting point of less than 220 ° C. The coalescence is a value measured under measurement conditions of a temperature of 230 ° C. and a load of 21.18N. The MFR of the 4-methylpentene-1 polymer can be adjusted to the above range by adjusting the type and composition ratio of the monomer constituting the 4-methylpentene-1 polymer and the regularity of the polymer. it can.

  The intrinsic viscosity [η] of the 4-methylpentene-1 polymer is preferably 0.5 or more, more preferably 0.6 or more, as measured in decalin at 135 ° C. The intrinsic viscosity [η] of the polymer is preferably 5.0 dl / g or less, more preferably 4.0 dl / g or less, and further preferably 2.5 dl / g or less. When the intrinsic viscosity [η] of the polymer is not more than the above upper limit, the coating suitability and the film forming property of the coating liquid are preferable because it is favorable, and when it is not less than the above lower limit, the shape stability of the resulting film is stable. It is preferable because it is easy to improve the properties. The method for measuring the intrinsic viscosity [η] is as described above. The intrinsic viscosity [η] of the polymer can be adjusted by the amount of hydrogen added in the polymerization step when the polymer is produced.

The density of the 4-methylpentene-1 series polymer is preferably 0.8 to 0.9 g · cm ⁻³ , more preferably 0.82 to 0.4 from the viewpoint of easily improving the heat resistance of the peelable film. a 85 g · ^{cm -3,} more preferably from 0.825~0.85g · ^{cm -3,} even more preferably 0.825~0.845g · ^{cm -3,} particularly preferably 0.825～ 0.84 g · cm ⁻³ . The density of the polymer can be measured according to JISK6268. The density of the polymer can be adjusted to the above range by adjusting the type and the composition ratio of the monomer constituting the 4-methylpentene-1 polymer.

  The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 4-methylpentene-1 polymer, is peeled off. From the viewpoint of easily improving the transparency, mechanical properties and surface smoothness of the conductive film, it is preferably 1.0 to 3.5, more preferably 1.3 to 3.0, and still more preferably 1.5 to 2.5. is there. The method for measuring the molecular weight distribution (Mw / Mn) is as described above. The value of the molecular weight distribution (Mw / Mn) can be adjusted according to the type of olefin polymerization catalyst, particularly a metallocene catalyst described later.

The crystallization temperature (T _c ) of the 4-methylpentene-1 polymer is preferably 80 to 190 ° C., more preferably 90 to 170 ° C., from the viewpoint of easily improving the moldability of the peelable film. The crystallization temperature of the polymer can be determined from the temperature at the peak apex of the crystallization peak measured by differential scanning calorimetry (DSC) in the same manner as the melting point (T _m ). The crystallization temperature of the polymer can be adjusted to the above range by adjusting the type and the composition ratio of the monomer constituting the 4-methylpentene-1 polymer.

  The 4-methylpentene-1 polymer can be produced by a conventionally known method. For example, you may manufacture by the method as described in Unexamined-Japanese-Patent No. 2013-227421, Unexamined-Japanese-Patent No. 2013-3205, etc. Commercially available products may be used as the 4-methylpentene-1 polymer (or a resin component containing the 4-methylpentene-1 polymer). For example, TPX (registered trademark) MX002 manufactured by Mitsui Chemicals, Inc. , TPX (registered trademark) DX845, TPX (registered trademark) EP0518, 4-methylpentene-1 resin EP1013 manufactured by Mitsui Chemicals, Inc. may be used. When the 4-methylpentene-1 polymer is a 4-methylpentene-1 copolymer, for example, in the presence of an olefin polymerization catalyst, carbon other than 4-methylpentene-1 and 4-methylpentene-1 It can be produced by polymerizing at least one olefin selected from the group consisting of α-olefins having 2 to 20 atoms and optionally other polymerizable monomers. Examples of the olefin polymerization catalyst include a metallocene catalyst and a Ziegler-Natta catalyst, and preferably a metallocene catalyst. Such metallocene catalysts include, for example, International Publication No. 01/53369, International Publication No. 01/27124, Japanese Unexamined Patent Publication No. 3-19396, Japanese Unexamined Patent Publication No. 02-41303, International Publication No. 06/025540. It is described in.

When the resin component is (1) 4-methylpentene-1 polymer A and (2) an olefin resin A ′ other than the 4-methylpentene-1 polymer A (in the case of (II) above) explain.
(1) Type of 4-methylpentene-1 series polymer A, proportion of structural units derived from 4-methylpentene-1, melting point, MFR, intrinsic viscosity, density, molecular weight distribution, crystallization temperature, production method, etc. The details of are the same as those described for the 4-methylpentene-1 polymer A in the case of (I).

  The (2) olefin resin A ′ is defined as a resin component different from the (1) 4-methylpentene-1 polymer A. That is, the (2) olefin resin A ′ does not contain a structural unit derived from 4-methyl-1-pentene.

  Specific examples of the (2) olefin resin A 'include ethylene polymers, propylene polymers, 1-butene polymers, cyclic olefin copolymers, chlorinated polyolefins, and the like. In the present invention, the (2) olefin resin A 'includes elastomers, copolymer rubbers and the like. The (2) olefin resin A ′ may contain one type of olefin resin or a combination of two or more types of olefin resins.

  The ethylene polymer is a polymer containing a structural unit derived from ethylene, and is an ethylene homopolymer (homopolyethylene) or an ethylene copolymer. The (2) olefin resin A ′ may contain one ethylene polymer as an ethylene polymer, or may contain a combination of two or more ethylene polymers. The proportion of the structural unit derived from ethylene in the ethylene polymer is not particularly limited, but from the viewpoint of transparency and mechanical properties of the film, preferably 80 mol% or more based on the total structural units constituting the ethylene polymer. More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more. Moreover, this ratio may be 100 mol% or less. The ethylene polymer includes polyethylene such as low density, medium density, high density, and high pressure method low density. Examples of the ethylene copolymer include an ethylene / α-olefin copolymer.

  The propylene-based polymer is a polymer containing a structural unit derived from propylene, and is a propylene homopolymer (homopolypropylene) or a copolymer of propylene. The (2) olefin resin A ′ may contain one type of propylene polymer as a propylene polymer, or may contain a combination of two or more types of propylene polymers. The proportion of the structural unit derived from propylene in the propylene-based polymer is not particularly limited, but from the viewpoint of transparency and mechanical properties of the film, preferably 80 mol% or more based on all structural units constituting the propylene-based polymer. More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more. Moreover, this ratio may be 100 mol% or less.

  The homopolypropylene is preferably an isotactic polypropylene homopolymer from the viewpoint of stereoregularity. The isotactic mesopentad fraction (mmmm) of isotactic polypropylene is preferably 92% or more, more preferably 93% or more, and still more preferably 94% or more. However, a syndiotactic polypropylene homopolymer may be used as the homopolypropylene.

  The isotactic mesopentad fraction (mmmm) is an index of stereoregularity that can be obtained by high-temperature Fourier transform nuclear magnetic resonance apparatus (high-temperature FT-NMR) measurement. Specifically, it can be measured using, for example, a high-temperature Fourier transform nuclear magnetic resonance apparatus (for example, “JNM-ECP500” manufactured by JEOL Ltd.). The observation nucleus is 13C (125 MHz). The measurement method by high-temperature FT-NMR is performed with reference to the method described in, for example, “Japan Analytical Chemistry / Polymer Analysis Research Council, New Edition Polymer Analysis Handbook, Kinokuniya, 1995, p. 610”. be able to. For example, measurement can be performed using measurement temperature, solvent, measurement mode, pulse width, pulse interval, number of integrations, and shift reference as described in the examples.

  The pentad fraction representing the degree of stereoregularity is a combination of pentads (mmmm and “meso (m)”) arranged in the same direction and “Rasemo (r)” arranged in the opposite direction. calculated as a percentage (%) based on the integrated value of the intensity of each signal derived from mrrm and the like. Each signal derived from mmmm, mrrm and the like can be assigned with reference to, for example, “T. Hayashi et al., Polymer, 29, 138 (1988)”.

  Examples of the copolymer of propylene include a copolymer of propylene and at least one olefin selected from the group consisting of ethylene and at least one α-olefin having 3 to 20 carbon atoms. The copolymer may be a random copolymer or a block copolymer. The olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms is, for example, ethylene, butene, pentene, hexene, etc., and the fact that ethylene is the film transparency, mechanical properties, and molding temperature. It is preferable from the viewpoint. The propylene-based polymer may be a copolymer containing one kind of olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms, or a copolymer containing two or more kinds of the above-mentioned olefins. It may be a coalescence. The olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms is also referred to as an olefin selected from the group consisting of an α-olefin having 2 to 20 carbon atoms.

  The copolymerization ratio of the olefin selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms in the copolymer of propylene is 5 based on the total amount of the propylene-based polymer from the viewpoint of the transparency of the film. The content is preferably not more than mass%, more preferably not more than 4 mass%.

  The melt flow rate (MFR) of the propylene polymer contained in the resin component is preferably 0.5 to 25 g / 10 minutes, more preferably 2 to 10 g / 10 minutes, from the viewpoint of moldability. The MFR is a value measured according to JIS K7210 under measurement conditions of a temperature of 230 ° C. and a load of 21.18N.

  The content of ash resulting from the polymerization catalyst residue contained in the propylene-based polymer contained in the resin component is preferably as small as possible from the viewpoint of easily reducing fine foreign matter (fish eye), more preferably It is 50 ppm or less, More preferably, it is 40 ppm or less. When the ash content is 50 ppm or less, fine foreign matters and defects are remarkably reduced, and contamination of electronic parts when the film of the present invention is used for electronic parts can be easily reduced.

  The content of the propylene-based polymer in the resin component is preferably 95 to 50% by mass, more preferably 85 to 85% based on the total amount of the resin component, from the viewpoint of easily satisfying both surface smoothness and releasability of the film. It is 50 mass%, More preferably, it is 80-50 mass%. In this case, the content of the 4-methylpentene-1 polymer in the resin component is preferably 5 to 50 based on the total amount of the resin component from the viewpoint of easily achieving both the surface smoothness and the release property of the film. It is 10 mass%, More preferably, it is 10-45 mass%, More preferably, it is 15-40 mass%.

The 1-butene polymer is a polymer containing a structural unit derived from 1-butene, and is a 1-butene homopolymer or a copolymer of 1-butene and another olefin different from 1-butene. is there. Examples of other olefins different from 1-butene include ethylene and α-olefins having 3 to 20 carbon atoms, specifically ethylene, propylene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1 -Octadecene etc. can be mentioned. The 1-butene polymer may contain a structural unit derived from one or more of these other olefins together with a structural unit derived from 1-butene. The 1-butene polymer is a copolymer of 1-butene and ethylene and / or propylene. From the viewpoint of miscibility between the 1-butene polymer and the 4-methylpentene-1 polymer. To preferred. The 1-butene polymer is preferably a copolymer having 30 to 90 mol% of 1-butene-derived structural units based on all structural units of the 1-butene polymer. Such 1-butene polymers are commercially available. Specifically, Tuffmer BL3450 (manufactured by Mitsui Chemicals), Tuffmer BL3450M (manufactured by Mitsui Chemicals), Tuffmer XM7070 (manufactured by Mitsui Chemicals), etc. Can be mentioned.
The resin component may contain one kind of 1-butene polymer as the 1-butene polymer, or may contain two or more kinds of 1-butene polymers in combination.

  When the resin component further contains a 1-butene polymer in addition to the propylene polymer and the 4-methylpentene-1 polymer, the propylene polymer and the 4-methylpentene-1 polymer It is preferable because it has an effect of promoting compatibilization and improving interlayer adhesion.

  The melt flow rate (MFR) of the 1-butene polymer is preferably 5 to 15 g / 10 minutes, more preferably 6 to 13 g / 10 minutes, from the viewpoint of film formability. The MFR is a value measured under conditions of a temperature of 230 ° C. and a load of 21.18 N according to JIS K7210.

  Examples of the cyclic olefin copolymer include cyclic olefins having 3 to 20 carbon atoms, preferably 5 to 15 carbon atoms (for example, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene. , Vinylcyclohexane, and the like).

  Ratio of structural units derived from 4-methylpentene-1 in the entire resin component (or the resin composition constituting the outermost layer) in the case of (II) above, melting point, MFR, intrinsic viscosity, density, molecular weight distribution, crystal About each detail, such as a conversion temperature, it replaces with the 4-methylpentene-1 type | system | group polymer A in the case of (I), and it is said that it is set as "the whole resin component (or resin composition which comprises outermost layer)". This is the same as described in (I).

The case where the resin component is a resin component different from the resin component of (1) 4-methylpentene-1 type polymer A, (3) (1) and (2) (in the case of (III) above) will be described. To do.
(1) Type of 4-methylpentene-1 series polymer A, proportion of structural units derived from 4-methylpentene-1, melting point, MFR, intrinsic viscosity, density, molecular weight distribution, crystallization temperature, production method, etc. The details of are the same as those described for the 4-methylpentene-1 polymer A in the case of (I).

  The thermoplastic resin component different from the (3) resin component, that is, the (1) 4-methylpentene-1 polymer A and the (2) olefin resin A ′, is a thermoplastic polyamide resin; Thermoplastic polyester resin; Thermoplastic vinyl aromatic resin; Thermoplastic polyurethane; Vinyl chloride resin; Vinylidene chloride resin; Acrylic resin; Ethylene / vinyl acetate copolymer; Ethylene / acrylic acid acrylate copolymer; Ethylene / methacrylic acid Acrylate copolymer; ionomer; ethylene vinyl alcohol copolymer; polyvinyl alcohol; fluororesin polycarbonate; polyacetal; polyphenylene oxide; polyphenylene sulfide polyimide; polyarylate; polysulfone; polyethersulfone; rosin resin; Resins and petroleum resins; copolymer rubber, and the like. The resin component (3) may contain one type, or may contain two or more types in combination.

  Ratio of structural units derived from 4-methylpentene-1 in the entire resin component (or resin composition constituting the outermost layer) in the case of (III) above, melting point, MFR, intrinsic viscosity, density, molecular weight distribution, crystal About each detail, such as a conversion temperature, it replaces with the 4-methylpentene-1 type | system | group polymer A in the case of (I), and it is said that it is set as "the whole resin component (or resin composition which comprises outermost layer)". This is the same as described in (I).

The case where the resin component is the resin component of (1), (2) and (3) (in the case of (IV) above) will be described.
(1) Type of 4-methylpentene-1 series polymer A, proportion of structural units derived from 4-methylpentene-1, melting point, MFR, intrinsic viscosity, density, molecular weight distribution, crystallization temperature, production method, etc. The details of are the same as those described for the 4-methylpentene-1 polymer A in the case of (I).
(2) Types of olefinic resins A ′ other than 4-methylpentene-1 type polymer A (including monomer types and amounts of components when a copolymer is included), MFR, isotactic meso Details of the pentad fraction, ash, and the like are the same as those described in (2) Olefin resin A ′ other than (2) 4-methylpentene-1 polymer A in the case of (II).
(3) The details of each of the (1) 4-methylpentene-1 type polymer A, the kind of thermoplastic resin component different from the (2) olefin type resin A ′, and the like in the case of (III) (3) This is the same as described for the thermoplastic resin component.
Ratio of structural units derived from 4-methylpentene-1 in the entire resin component (or the resin composition constituting the outermost layer) in the case of (IV) above, melting point, MFR, intrinsic viscosity, density, molecular weight distribution, crystal About each detail, such as a conversion temperature, it replaces with the 4-methylpentene-1 type | system | group polymer A in the case of (I), and it is said that it is set as "the whole resin component (or resin composition which comprises outermost layer)". This is the same as described in (I).

Here, specific examples will be described below. Use of the following [1] to [6] as the resin component constituting the outermost surface layer (or the resin composition constituting the outermost layer) is preferable as an embodiment of the present invention. In addition, the resin components of [1] to [6] below may be used as occupying all of the resin components constituting the outermost surface layer, or occupy a part of the resin components constituting the outermost surface layer. It may be used as a thing. In addition, as the resin component, one or more of the resin components [1] to [6] below may be used in combination.
[1] Structural unit (i) derived from 4-methylpentene-1 5 to 95 mol%, at least one α selected from α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1 -Consists of 5 to 95 mol% of structural units derived from olefin (ii) and 0 to 10 mol% of structural units derived from non-conjugated polyene (iii) (provided that structural units (i), (ii) and (iii) 4-methylpentene-1α-olefin copolymer)
[2] Structural unit (i) derived from 4-methylpentene-1 33 to 80 mol%, at least one α selected from α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1 -Structural unit derived from olefin (ii) 67 to 20 mol% and structural unit derived from non-conjugated polyene (iii) 0 to 10 mol% (provided that total of structural units (i), (ii) and (iii) 4-methylpentene-1, α-olefin copolymer (A) comprising 50 to 95 parts by weight, and thermoplastics other than the 4-methylpentene-1, α-olefin copolymer 4 to 50 parts by weight of the resin (B) (provided that the total of the copolymer (A) and the thermoplastic resin (B) is 100 parts by weight), 4-methylpentene-1, α-olefin Copolymer composition,
[3] 50 to 98 parts by weight of 4-methylpentene-1 copolymer (AA), crystalline olefin resin (BB) other than 4-methylpentene-1 copolymer (AA) (for example, melting point is 100 ° C. 1 to 49 parts by weight of the α-olefin copolymer (CC) having a melting point of less than 100 ° C. other than 1 to 49 parts by weight and the 4-methylpentene-1 copolymer (AA). 49 parts by weight (provided that the total of (AA), (BB) and (CC) is 100 parts by weight), and the copolymer (AA) has the following requirement (a-1):
(A-1) The structural unit derived from 4-methylpentene-1 is 5 to 95% by weight, and at least one selected from α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1 The structural unit derived from the α-olefin is 5 to 95% by weight (provided that the total amount of the structural unit in the copolymer (AA) is 100% by weight).
4-methylpentene-1, α-olefin copolymer composition,
[4] Structural unit (i) derived from 4-methylpentene-1 5 to 95 mol%, at least one α selected from α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1 -Consists of 5 to 95 mol% of structural units derived from olefin (ii) and 0 to 10 mol% of structural units derived from non-conjugated polyene (iii) (provided that structural units (i), (ii) and (iii) 4 to 95 parts by weight of 4-methylpentene-1 / α-olefin copolymer and a thermoplastic resin other than the 4-methylpentene-1 / α-olefin copolymer (B 4) to 95 parts by weight (provided that the total of the copolymer and the thermoplastic resin (B) is 100 parts by weight). Polymer composition,
[5] Structural unit (i) derived from 4-methylpentene-1 33 to 80 mol%, at least one α selected from α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1 -Structural unit derived from olefin (ii) 67 to 20 mol% and structural unit derived from non-conjugated polyene (iii) 0 to 10 mol% (provided that total of structural units (i), (ii) and (iii) 4-methylpentene-1, α-olefin copolymer (A) 5 to 49 parts by weight, and thermoplastics other than the 4-methylpentene-1, α-olefin copolymer Resin (B) 51-95 parts by weight (provided that the total of the copolymer (A) and the thermoplastic resin (B) is 100 parts by weight) 4-methylpentene-1 · α-olefin copolymer composition,
[6] 50-96 parts by weight of 4-methylpentene-1 copolymer (AA), crystalline olefin resin (BB) other than 4-methylpentene-1 copolymer (AA) (for example, melting point is 100 ° C. Α-olefin copolymer (CC) having a melting point other than 2-45 parts by weight (BB) and 4-methylpentene-1 copolymer (AA) (including the above crystalline olefin resin) and less than 100 ° C. 2 to 45 parts by weight (provided that the total of (AA), (BB) and (CC) is 100 parts by weight),
The copolymer (AA) has the following requirement (c-1):
(C-1) The structural unit derived from 4-methylpentene-1 is 18 to 90% by weight, and is at least one selected from α-olefins having 2 to 20 carbon atoms excluding 4-methylpentene-1. The structural unit derived from the α-olefin is 10 to 82% by weight (provided that the total amount of the structural unit in the copolymer (AA) is 100% by weight).
The 4-methylpentene-1 copolymer composition satisfying

Examples of the non-conjugated polyene in [1], [2], [4] and [5] include non-conjugated polyene having 5 to 20 carbon atoms (preferably 5 to 10). 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5 -Hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene , Dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2 Norbornene, 5-vinylidene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3 -Isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like can be mentioned.
As the thermoplastic resin (B) in [2], [4] and [5], for example, (2) the olefin resin A ′, (3) different from the resin components of (1) and (2) above. The thermoplastic resin etc. which were illustrated in the resin component are mentioned.
The crystalline olefin resin in [3] and [6] is, for example, a resin having a melting point of 70 ° C. or higher in a differential scanning calorimeter.
Examples of the α-olefin in [1] to [6] include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene and 1-tetradecene. , 1-hexadecene, 1-octadecene, 1-eicosene and the like, a linear α-olefin having 2 to 20, preferably 2 to 15 and more preferably 2 to 10 carbon atoms.

  For example, the outermost layer is formed by coating a coating liquid containing a resin component containing 4-methylpentene-1 polymer A and at least one solvent on the intermediate layer, and from the obtained coating layer. Formed by removing the solvent.

  The solvent is not particularly limited as long as the resin component containing 4-methylpentene-1 polymer A can be dissolved. For example, aromatic hydrocarbons such as toluene and xylene, n-heptane, methylcyclohexane and the like can be used. Organic solvents such as aliphatic hydrocarbons can be mentioned. The boiling point of the solvent is preferably 10 to 150 ° C., more preferably 20 to 120 ° C., from the viewpoint of easily improving the handling properties of the coating liquid and the production efficiency of the peelable film.

  The concentration of the resin component containing 4-methylpentene-1 polymer A in the coating solution is 1 to 10% by mass based on the total amount of the coating solution from the viewpoint of the stability of the coating solution and the coating suitability. It is preferable that it is 3-7 mass%. The coating method is not specifically limited, The coating method described about the intermediate | middle layer can be used similarly.

  As a method for removing the solvent from the coating layer, the method described for the intermediate layer can be similarly used.

  The thickness of the outermost layer is preferably 0.1 μm or more, more preferably 0.3 μm or more, and particularly preferably 0.5 μm or more from the viewpoint of easily improving peelability. The thickness of the outermost layer is preferably 3.0 μm or less, and more preferably 1.5 μm or less, from the viewpoint of coating suitability and ease of production. The thickness of the outermost layer is measured by a light interference method using a surface / layer cross-sectional shape measuring instrument (for example, “VertScan (registered trademark) 2.0” manufactured by Ryoka Systems Inc.).

  The base material layer, the intermediate layer, and the outermost layer may contain at least one additive as necessary. Examples of the additive include stabilizers such as antioxidants, chlorine absorbers, ultraviolet absorbers, lubricants, plasticizers, flame retardants, antistatic agents, colorants, antiblocking agents and the like. You may add such an additive to a base material layer, an intermediate | middle layer, or an outermost layer within the range which does not impair the effect of this invention. At least one additive may be contained only in any one of the base material layer, the intermediate layer, and the outermost layer, or may be contained in all the base material layer, the intermediate layer, and the outermost layer. Moreover, the base material layer, the intermediate layer, and the outermost layer may contain the same or different additives.

“Antioxidant” has a role as a primary agent formulated for the purpose of suppressing deterioration due to heat and oxidation during the production of a peelable film, and for the purpose of suppressing deterioration over time when used for a long time. At least as a secondary agent. Depending on these roles, different types of antioxidants may be used, or one type of antioxidant may have two roles.
When different types of antioxidants are used, for example, a primary agent intended to prevent deterioration during production such as deterioration in a molding machine, for example, 2,6-di-tert-butyl-p-cresol (General name: BHT) is preferably added in an amount of about 1000 to 3000 ppm in the composition for obtaining each layer. Most of the antioxidant blended for this purpose is consumed in the molding process and hardly remains in the peelable film. Therefore, generally the remaining amount is less than 100 ppm, which is preferable in that the adherend is hardly contaminated by the antioxidant.
As the secondary agent, known antioxidants can be used, and examples thereof include phenol-based, hindered amine-based, phosphite-based, lactone-based, and tocopherol-based thermal stabilizers and antioxidants. Specifically, dibutylhydroxytoluene, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-t-butyl-4hydroxy) benzene, tris (2,4-di-t-butylphenyl) phosphite and the like can be mentioned. More specifically, Irganox, an antioxidant manufactured by BASF Japan Ltd.
(Registered trademark) 1010, Irganox (registered trademark) 1330, and Irgafos (registered trademark) 168.
Among them, at least one selected from phenolic antioxidants or a combination thereof, a combination of phenolic and phosphite, a combination of phenolic and lactone, a combination of phenolic, phosphite and lactone However, the effect which suppresses deterioration with time at the time of using a film for a long term can be provided, and it is preferable.
Moreover, you may use phosphorus antioxidant as a secondary agent. Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite (trade name: Irgafos (registered trademark) 168), bis (2,4-di-t-butyl-6- 6). Methylphenyl) ethyl phosphite (trade name: Irgafos (registered trademark) 38) and the like.
The content of the antioxidant as the secondary agent is preferably from 300 ppm to 2500 ppm, more preferably from 500 ppm to 1500 ppm, based on the total amount of resin contained in each layer. By making it 300 ppm or more, it is easy to give the effect of suppressing deterioration over time when the film is used for a long time, and by making it 2500 ppm or less, it is easy to prevent contamination of the adherend by the antioxidant.

  The “chlorine absorbent” is not particularly limited, and examples thereof include metal soaps such as calcium stearate.

  The “ultraviolet absorber” is not particularly limited, and examples thereof include benzotriazole (such as Tinuvin 328 manufactured by BASF), benzophenone (such as Cysorb UV-531 manufactured by Cytec), and hydroxybenzoate (UV-CHEK-AM-340 manufactured by Ferro) and the like. Can be mentioned.

  The “lubricant” is not particularly limited. For example, a primary amide (such as stearic acid amide), a secondary amide (such as N-stearyl stearic acid amide), ethylene bisamide (N, N′-ethylene bis-stearic acid amide) Etc.).

  The “plasticizer” is not particularly limited, and examples thereof include a PP random copolymer.

  The “flame retardant” is not particularly limited, and examples thereof include halogen compounds, aluminum hydroxide, magnesium hydroxide, phosphates, borates, and antimony oxides.

  The “antistatic agent” is not particularly limited, and examples thereof include glycerin monoesters (such as glycerin monostearate) and ethoxylated secondary amines.

  The “colorant” is not particularly limited, and examples thereof include cadmium and chromium-containing inorganic compounds to azo and quinacridone organic pigments.

  “Anti-blocking agent” is not particularly limited as long as it is added to prevent blocking and exhibits an effect as a nucleating agent. For example, silica particles, alumina, (synthetic) zeolite, calcium carbonate, kaolin, talc, mica, oxidation Inorganic pigments such as zinc, magnesium oxide, quartz, magnesium carbonate, parium sulfate, titanium dioxide, polystyrene, polyacrylic particles, polymethyl methacrylate (PMMA) particles, crosslinked polyethylene particles, polyester, polyamide, polycarbonate, polyether, Polyethersulfone, polyetherimide, polyphenylene sulfide, polyetheretherketone, polyamideimide, (crosslinked) melamine resin, benzoguanamine resin, urea resin, amino resin, furan resin, epoxy resin, phenol resin Lumpur resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, polyimide resin, fatty acid amides, and organic pigments such as fatty acid glycerol ester compound. The antiblocking agent is preferably a pigment having a particle diameter of 0.1 μm to 10 μm, and PMMA and silica particles are more preferable because they are excellent in blocking resistance and slipping property. For example, by including such a pigment in the base material layer, the slipperiness of the front and back surfaces of the base material layer is improved, and blocking can be suppressed.

  You may provide the surface of the peelable film of this invention with the fine surface roughness which improves winding suitability in the range which does not have trouble in bonding in the case of using as a peelable film. As a method for giving fine irregularities on the film surface, various known roughening methods such as an embossing method and an etching method can be employed, and among them, a roughening using β crystals that do not require the incorporation of impurities, etc. The surface method is preferred. The production rate of β crystals can be generally controlled by changing the casting temperature and the casting speed. In addition, the melting / transition ratio of the β crystal can be controlled by the roll temperature in the longitudinal stretching process, and fine roughening can be achieved by selecting optimum production conditions for these two parameters of β crystal formation and its melting / transition. Surface property can be obtained.

  The protruding peak height (Rpk) in the load curve obtained from the roughness curve of the film surface on the outermost layer side of the peelable film of the present invention is preferably 0.04 μm or less from the viewpoint of enhancing the smoothness of the peelable film. More preferably, it is 0.03 micrometer or less, More preferably, it is 0.02 micrometer or less. The protruding peak height (Rpk) is usually 0.005 μm or more, preferably 0.008 μm or more.

  The protruding peak height (Rpk) is JISB-0671-2: 2002, which is the average height of the protruding peak above the core of the roughness curve, calculated from the height characteristics of the linear load curve. It is an index that makes it possible to accurately determine the state of protruding protrusions, that is, abnormal protrusions, which have a large influence on the contact with the adherend while removing the influence of continuous undulations on the film surface. is there.

  The protruding peak height (Rpk) can be measured by a contact method using a stylus, a visible light reflection, a non-contact method using laser light interference, an atomic force phase difference measurement using a scanning probe microscope (SPM / AFM), or the like. it can.

  Such an Rpk value means the average height of the abnormal protrusions that protrude outside the core portion of the roughness curve, and the larger this value, the more abnormal protrusions on the film surface, that is, the biting on the adherend. Is a shape that tends to cause sticking that causes a large peeling force. When this value is small, the protruding peak portion having few abnormal protruding portions and hardly sticking to the adherend has a smooth plateau structure, which is preferable as the surface of the film for peeling.

The T-peel peeling force (300 mm / min) on the polyester adhesive tape on the film surface on the outermost layer side of the peelable film of the present invention is preferably 0 from the viewpoint of easily improving the adhesion of the peelable film to the adherend. 0.1 N / 25 mm or more, more preferably 0.15 N / 25 mm or more, still more preferably 0.2 N / 25 mm or more, and particularly preferably 1 N / 25 mm or more. The film surface on the outermost layer side of the peelable film of the present invention has a T-peel peel force (300 mm / min) with respect to the polyester adhesive tape, preferably from 2.0 N / 25 mm or less, from the viewpoint of easily improving peelability. More preferably, it is 1.5 N / 25 mm or less, More preferably, it is 1.3 N / 25 mm or less, Most preferably, it is 1.2 N / 25 mm or less. The T-peel peeling force of the peelable film is a polyester adhesive tape having a width of 50 mm and a length of 200 mm on the surface of the outermost layer of the peelable film (Nitto Denko Corporation NO.31B tape, acrylic adhesive). Is applied by reciprocating a 2 kg roller twice to obtain a pre-processed adhesive product, and then the adhesive product is heated at 23 ° C. for 2 minutes, and a weight is applied so that a load of 5 KPa is obtained. A sample cut out to a width of 25 mm from a film obtained by allowing it to stand for 20 hours in an environment of 23 ° C. and 50% humidity is used as a measurement sample, and a tensile tester (for example, Kyowa Interface Science Co., Ltd., adhesive -It measures as peeling force at the time of performing T-peel peeling at a speed of 300 mm / min using a film peeling analyzer VP-2). In the present invention, and also referred to herein as convenience P _A the release force.

The T-peel peeling force (1000 mm / min) to the polyester adhesive tape on the film surface on the outermost layer side of the peelable film of the present invention is preferably 0 from the viewpoint of easily improving the adhesion of the peelable film to the adherend. 0.05 N / 25 mm or more, more preferably 0.08 N / 25 mm or more, further preferably 0.1 N / 25 mm or more, and particularly preferably 0.4 N / 25 mm or more. The film surface on the outermost layer side of the peelable film of the present invention has a T-peel peel strength (1000 mm / min) with respect to the polyester adhesive tape, preferably from 2.0 N / 25 mm or less, from the viewpoint of easily improving peelability. More preferably, it is 1.5 N / 25 mm or less, More preferably, it is 1.3 N / 25 mm or less, Most preferably, it is 1 N / 25 mm or less. The above-described T-peel peel force (300 mm / min) is measured except that the T-peel peel force (1000 mm / min) of the peelable film is 1000 mm / min instead of 300 mm / min. It is the same as the method. In the present invention, and also referred to herein as convenience P _B the release force.

The T-peel peeling force (10000 mm / min) to the polyester adhesive tape on the film surface on the outermost layer side of the peelable film of the present invention is preferably 0 from the viewpoint of easily improving the adhesion of the peelable film to the adherend. 0.01 N / 25 mm or more, more preferably 0.03 N / 25 mm or more, still more preferably 0.05 N / 25 mm or more, and particularly preferably 0.1 N / 25 mm or more. The T-peel peeling force (10000 mm / min) on the polyester adhesive tape on the film surface on the outermost layer side of the peelable film of the present invention is preferably 1.7 N / 25 mm or less from the viewpoint of easily improving peelability. More preferably, it is 1.3 N / 25 mm or less, More preferably, it is 1.1 N / 25 mm or less, Most preferably, it is 1 N / 25 mm or less. The above-described T-peel peel force (300 mm / min) is measured except that the T-peel peel force (10000 mm / min) of the peelable film is 10000 mm / min instead of the speed of 300 mm / min. It is the same as the method. In the present invention, and also referred to herein as convenience P _C the peel force.

The T-peel peeling force (300 mm / min) on the polyester adhesive tape on the film surface on the outermost layer side of the peelable film after performing the heat treatment at 110 ° C. on the peelable film of the present invention is peelable. From the viewpoint of easily improving the adhesion of the film to the adherend, preferably 0.1 N / 25 mm or more, more preferably 0.15 N / 25 mm or more, still more preferably 0.2 N / 25 mm or more, and particularly preferably 1 N / 25 mm or more. It is. The film surface on the outermost layer side of the peelable film of the present invention has a T-peel peel force (300 mm / min) with respect to the polyester adhesive tape, preferably from 2.0 N / 25 mm or less, from the viewpoint of easily improving peelability. More preferably, it is 1.5 N / 25 mm or less, More preferably, it is 1.3 N / 25 mm or less, Most preferably, it is 1.2 N / 25 mm or less. The measuring method of the T peel peel force (300 mm / min) of the peelable film is the above T peel peel force (300 mm) except that the heat treatment for 2 minutes is 110 ° C. instead of 23 ° C. / Min). In the present invention and this specification, the peeling force is also referred to as P _A ′ for convenience.

The T-peel peeling force (1000 mm / min) on the polyester adhesive tape on the film surface on the outermost layer side of the peelable film after the heat treatment at 110 ° C. is performed on the peelable film of the present invention is peelable. From the viewpoint of easily improving the adhesion of the film to the adherend, it is preferably 0.05 N / 25 mm or more, more preferably 0.08 N / 25 mm or more, further preferably 0.1 N / 25 mm or more, particularly preferably 0.4 N / It is 25 mm or more. The film surface on the outermost layer side of the peelable film of the present invention has a T-peel peel strength (1000 mm / min) with respect to the polyester adhesive tape, preferably from 2.0 N / 25 mm or less, from the viewpoint of easily improving peelability. More preferably, it is 1.5 N / 25 mm or less, More preferably, it is 1.3 N / 25 mm or less, Most preferably, it is 1 N / 25 mm or less. The measuring method of the T peel peel force (1000 mm / min) of the peelable film is the above T peel peel force (1000 mm) except that the heat treatment for 2 minutes is performed at a temperature of 110 ° C. instead of a temperature of 23 ° C. / Min). In the present invention and this specification, the peeling force is also referred to as P _B ′ for convenience.

The T-peel peeling force (10000 mm / min) to the polyester adhesive tape on the film surface on the outermost layer side of the peelable film after the heat treatment at 110 ° C. is performed on the peelable film of the present invention is peelable. From the viewpoint of easily improving the adhesion of the film to the adherend, it is preferably 0.01 N / 25 mm or more, more preferably 0.03 N / 25 mm or more, still more preferably 0.05 N / 25 mm or more, and particularly preferably 0.1 N / It is 25 mm or more. The T-peel peeling force (10000 mm / min) on the polyester adhesive tape on the film surface on the outermost layer side of the peelable film of the present invention is preferably 1.7 N / 25 mm or less from the viewpoint of easily improving peelability. More preferably, it is 1.3 N / 25 mm or less, More preferably, it is 1.1 N / 25 mm or less, Most preferably, it is 1 N / 25 mm or less. The measuring method of the said T-peel peeling force (10000 mm / min) of a peelable film is the above-mentioned T-peel peeling force (10000 mm) except that the temperature is 110 ° C. instead of 23 ° C. for the heat treatment for 2 minutes. / Min). In the present invention, and also referred to herein as convenience P _{C 'the} release force.

_P B / _{P A} values of the peelable film of the present invention is preferably from 0.1 to 0.7, more preferably 0.2 to 0.5, more preferably 0.3 to 0.45. When the P _B / P _A value is within the above range, both workability such as transporting a release film roll and workability in a high speed region (for example, 1000 mm / min or more, 3000 mm / min or more) are achieved. be able to.

_P C / _{P A} values of the peelable film of the present invention is preferably from 0.05 to 0.6, more preferably 0.1 to 0.5, more preferably 0.2 to 0.4. When the P _C / P _A value is within the above range, both workability such as transporting a release film roll and workability in an ultra-high speed region (eg, 5000 mm / min or more, 10000 mm / min or more, etc.) are compatible. can do.

_{P A} '/ _{P A} values of the peelable film of the present invention is preferably 0.9 to 1.1. When the P _A ′ / P _A value is within the above range, it is difficult to be affected by the surrounding temperature change, and the workability such as transporting the release film roll is good, which is preferable.

_{P B} '/ _{P B} value of the release film of the present invention is preferably 0.9 to 1.1. P _B '/ P _B value within the above range makes it difficult to be affected by temperature changes in the storage environment and processing environment, and stable processing in a high-speed region (eg, 1000 mm / min or more, 3000 mm / min or more). It is preferable that

, _{P C} '/ _{P C} value of the release film of the present invention is preferably 0.9 to 1.1. By _{P C} '/ P _C value is within the above range, less susceptible to temperature changes in storage environment and processing environment, ultra-high-speed region (e.g., 5000 mm / min or more, such as 10000 mm / min or more) stable in Workability can be obtained, which is preferable

  The thickness of the peelable film of the present invention is preferably 18 μm or more, more preferably 20 μm or more, from the viewpoint of handleability as a peelable film. The thickness of the peelable film is preferably 100 μm or less and more preferably 50 μm or less from the viewpoint of handleability as a peelable film. The thickness of the peelable film of the present invention is measured according to JIS C-2151 using a micrometer (JIS B-7502).

  The haze of the peelable film of the present invention is preferably 10.5% or less, more preferably 8% or less, still more preferably 5% or less, and particularly preferably 4% or less. The haze value (cloudiness) can be measured using a known haze meter or the like. A film having a high haze value (cloudiness) (in general, in the case of a thin film having a low internal haze) shows a rough surface.

The peelable film of the present invention is excellent as a film for peeling because it has good peelability when peeled at a low speed and also has good peelability when peeled at a high speed. . For example, the film of the present invention is effective as a peeling application at a high speed such as 1000 mm / min or more, 3000 mm / min or more, 5000 mm / min or more, or 10,000 mm / min or more.
The peelable film of the present invention has a stable peel force regardless of the heat treatment temperature. Therefore, the film of the present invention is also preferably used when used in an environment at a high temperature (in other words, for example, when used for peeling in an environment of 100 ° C. or higher).

The peelable film of the present invention is suitably used as a peelable film used for a surface protective film, an adhesive tape, and the like, a release liner or a separator film, and a carrier for producing a composite material.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, “parts” and “%” represent “parts by mass” and “% by mass”, respectively.

[Measurement method and evaluation method]
Various measurement methods and evaluation methods in Examples and Comparative Examples are as follows.

[Melt flow rate at 230 ° C.]
According to JISK-7210 (1999), the measurement was performed under conditions of a temperature of 230 ° C. and a load of 21.18 N.

[Melting point]
The melting point of the resin component was calculated by the following procedure using an input compensated DSCD diamond DSC manufactured by Perkin Elmer.
First, 2 mg of the resin component was weighed, packed in an aluminum sample holder, set in a DSC apparatus, heated from 0 ° C. to 280 ° C. at a rate of 10 ° C./min under a nitrogen flow, and held at 280 ° C. for 5 minutes. After cooling to 30 ° C. at 30 ° C./min, the endothermic peak when the temperature was raised again to 280 ° C. at 10 ° C./min was taken as the melting point.

[Acid Value of Polyolefin Resin B1 Having Carboxyl Group]
It measured by the method based on JIS0070 (neutralization titration method).

[Hydroxyl value of polyolefin resin B2 having a hydroxyl group]
It measured by the method based on JIS0070 (neutralization titration method).

[Thickness of intermediate layer and outermost layer]
Measuring instrument: Ryoka System Co., Ltd. optical interference method surface / layer cross-sectional shape measuring instrument VertScan (registered trademark) 2.0
In the layer thickness measurement mode (bearing measurement) of the measuring machine, the optical distance of each layer is obtained from the refractive index of 1.60 of the base material layer and the refractive index of 1.48 of the intermediate layer and outermost layer, and the thickness of the intermediate layer and outermost layer. Was measured.

[Thickness of base material layer and film]
The thickness of the peelable film and the base material layer was measured based on JIS C-2151 using a micrometer (JIS B-7502).

[Degree of haze]
The sample cut into 50 mm x 100 mm was measured using Nippon Denshoku Co., Ltd. haze meter NDH-5000. The number of measurements was 3, and the average value was adopted.

[Projection peak height (Rpk)]
Measuring instrument: Ryoka System Co., Ltd. optical interference method surface / layer cross-sectional shape measuring instrument VertScan (registered trademark) 2.0
Of the core part level difference (Rk), protruding peak height Rpk, and protruding valley part depth (Rvk) specified in JIS B-0671-2: 2002, the core part level difference (Rk) and the protruding peak part Height (Rpk) was used as an index.

[Surface strength (1)]
Nitto Denko Corporation NO. An index of the surface strength of the peelable film by evaluating the transferability of the outermost layer to the peeled polyester tape at the time of measuring the T-peel peel strength using 31B tape (polyester tape with an acrylic pressure-sensitive adhesive). It was.
◯: No transition of the outermost layer to the peeled polyester tape is observed.
Δ: A part of the outermost layer was transferred to the peeled polyester tape.
X: The outermost layer completely transferred to the peeled polyester tape.
[Surface strength (2)]
Nitto Denko Corporation NO. The transferability of the outermost layer to the peeled polyester tape at the time of measuring the T-peel peel strength using a 31D tape (polyester tape with rubber-based adhesive) was determined as NO. Evaluation was made according to the same criteria as for 31B tape, and was used as an index of the surface strength of the peelable film.

[T-peel peel strength (23 ℃ treatment)]
A polyester adhesive tape (Nitto Denko Corporation NO.31B tape, acrylic adhesive) with a width of 50 mm and a length of 200 mm is applied to the outermost film surface of the peelable film by reciprocating a 2 kg roller twice. A pre-treatment patch was obtained.
Subsequently, the patch was heat-treated at 23 ° C. for 2 minutes. In the heat treatment, a hot air dryer was used.
Next, a weight was placed on the attached product so as to have a load of 5 KPa, and it was allowed to stand at 23 ° C. in an environment of 50% humidity for 20 hours.
Samples obtained by cutting the obtained patch after treatment to a width of 25 mm were used as measurement samples, and using a peeling tester (Kyowa Interface Science Co., Ltd., Adhesive / film peeling analyzer VP-2), (i) 300 mm / T-peel peeling test was performed at each speed of min, (ii) 1000 mm / min, and (iii) 10000 mm / min, and the peeling force at that time was measured. Each measurement was performed three times, and the average value was defined as the T-peel peel strength (23 ° C. treatment) of each peelable film.

[T-peel peel strength (110 ℃ treatment)]
About the heat processing for 2 minutes, except having changed temperature into 110 degreeC instead of 23 degreeC, it carried out similarly to the said [T-peel peeling force (23 degreeC process)], and obtained the post-processing patch. Samples obtained by cutting the patch after treatment to a width of 25 mm were used as measurement samples, and (i) 300 mm / min, using a peeling tester (manufactured by Kyowa Interface Science Co., Ltd., adhesive / film peeling analyzer VP-2). (ii) A T-peel peel test was performed at each speed of 1000 mm / min and (iii) 10,000 mm / min, and the peel force at that time was measured. Each measurement was performed three times, and the average value was defined as the T-peel peel strength (110 ° C. treatment) of each peelable film.

〔specific gravity〕
First, each resin component (EP1013, Tuffmer XM7070, Syxen NC, COC8007, Elitel UE3200, Cybinol EK108, S-Rec BL-S) was used and dispersed in toluene to a concentration of 4% by mass. Subsequently, using a reflux apparatus, the dispersion was stirred at 110 ° C. for 1 hour to dissolve each resin component, and the solution was cooled. Thereby, the coating liquid A (for forming the outermost layer) was obtained.
Next, the coating liquid A was dropped on a polytetrafluoroethylene plate and dried for 20 hours to produce a resin film.
Next, the resin film was peeled from the polytetrafluoroethylene plate.
Next, the specific gravity of each resin film was measured using a gas displacement density measuring device (Accumic II 1340, manufactured by Micromeritics).

〔Glass-transition temperature〕
Each resin film was obtained in the same manner as in the above [specific gravity] measurement.
Next, the glass transition temperature of the resin film was measured using a differential scanning calorimeter (Diamond DSC, manufactured by Perkin Elmer Co.) in accordance with JIS 7121. Specifically, 5 mg of the resin film is packed in an aluminum pan, heated to 200 ° C., held at 200 ° C. for 5 minutes, cooled to −40 ° C. at 10 ° C./min, and held at −40 ° C. for 5 minutes. After that, it was obtained from an endothermic curve when the temperature was raised at 10 ° C./min.

Example 1
A special polyolefin resin ("Surflen (registered trademark) P-1000" manufactured by Mitsubishi Chemical Corporation, maleated hydrogenated styrene-butadiene-styrene block copolymer) was used and diluted with toluene to a concentration of 2% by mass. . Thereby, the coating liquid B for forming an intermediate | middle layer was obtained.
Next, as a resin component constituting the outermost layer, a resin A1 “EP1013” containing a 4-methylpentene-1 polymer containing a structural unit derived from 4-methylpentene-1 (MFR Chemicals, MFR) = 10 g / 10 min (temperature 230 ° C., load 21.18 N), melting point 130 ° C., specific gravity 0.834 g · cm ⁻³ , glass transition temperature 40 ° C.), dispersed in toluene to a concentration of 4% by mass I let you. Next, using a reflux apparatus, the dispersion was stirred at 110 ° C. for 1 hour to dissolve the 4-methylpentene-1 polymer, and the solution was further cooled. Thereby, the coating liquid A for forming the outermost layer was obtained.
Next, a biaxially stretched polyethylene terephthalate film (“Diafoil T100” manufactured by Mitsubishi Plastics, Inc.) having a thickness of 38 μm was used as the base material layer. Next, the coating liquid B was applied onto the base material layer using a Mayer bar and dried at 110 ° C. for 1 minute in an explosion-proof dryer, and the base material layer and the intermediate layer (thickness: 0.2 μm) ) Was obtained.
Next, on the intermediate layer of the obtained laminate, the coating liquid A was applied using a Meyer bar, and dried at 110 ° C. for 1 minute in an explosion-proof dryer, and the outermost layer (thickness: 0.5 μm) ) Was formed. This obtained the peelable film which has a base material layer, an intermediate | middle layer, and an outermost layer.

Comparative Example 1
As a resin component constituting the outermost layer, instead of 4-methylpentene-1 polymer-containing resin A1 “EP1013”, α-olefin copolymer “Tuffmer XM7070” (manufactured by Mitsui Chemicals, Inc., specific gravity 0.88 g · A peelable film was obtained by the same method as in Example 1 except that cm ⁻³ , glass transition temperature −15 ° C.) was used.

Comparative Example 2
As a resin component constituting the outermost layer, instead of 4-methylpentene-1 polymer-containing resin A1 “EP1013”, polyolefin “Zyxen NC” (manufactured by Sumitomo Seika Co., Ltd., specific gravity 0.94 g · cm ⁻³ , A peelable film was obtained by the same method as in Example 1 except that the glass transition temperature was −50 ° C.

Comparative Example 3
As a resin component constituting the outermost layer, instead of 4-methylpentene-1 polymer-containing resin A1 “EP1013”, a cyclic olefin copolymer “COC8007” manufactured by Topas Advanced Polymers, specific gravity 1.01 g · cm ^{− 3} and a glass transition temperature of 78 ° C.) was used to obtain a peelable film by the same method as in Example 1.

Comparative Example 4
As a resin component constituting the outermost layer, instead of 4-methylpentene-1 polymer-containing resin A1 “EP1013”, a cyclic olefin copolymer “Eritel UE3200” manufactured by Unitika Ltd., specific gravity 1.25 g · cm ^{− 3} and a glass transition temperature of 65 ° C.) was used to obtain a peelable film by the same method as in Example 1.

Comparative Example 5
As a resin component constituting the outermost layer, instead of the 4-methylpentene-1 polymer-containing resin A1 “EP1013”, an acrylic resin “Cybinol EK108” manufactured by Seiden Chemical Co., Ltd., specific gravity 1.19 g · cm ⁻³ , glass transition A peelable film was obtained in the same manner as in Example 1 except that the temperature was 56 ° C.

Comparative Example 6
As a resin component constituting the outermost layer, instead of 4-methylpentene-1 polymer-containing resin A1 “EP1013”, a polyacetal resin “ESREC BL-S” manufactured by Sekisui Chemical Co., Ltd., specific gravity 1.42 g · cm ⁻³ A peelable film was obtained in the same manner as in Example 1 except that a glass transition temperature of 61 ° C. was used.

(A) Specific gravity of the outermost layer of each peelable film obtained in Example 1 and Comparative Examples 1 to 6, (b) Glass transition temperature (Tg) of the outermost layer, (c) T-peel peeling force (23 ° C. treatment) ), (D) Table 1 shows the results of T-peel peeling force (110 ° C. treatment). Also,
(e) 23 ° C. after treatment of the release rate of 300 mm / min to _P A (T-shape peeling strength at a peeling speed of 300 mm / min in the above (c)) T-shape peeling force when the,
(f) T-peel peeling force at a peeling rate of 1000 mm / min after 23 ° C. treatment (T-peel peeling force at a peeling rate of 1000 mm / min in the above (c)) is expressed as P _B ,
(g) T-peel peeling force at a peeling speed of 10000 mm / min after 23 ° C. treatment (T-peel peeling force at a peeling speed of 10,000 mm / min in the above (c)) is expressed as P _C ,
(h) T-shape peeling strength at a peeling speed of 300 mm / min after 110 ° C. treatment (the (T-shape peeling strength at a peeling speed of 300 mm / min in d)) the _{P A} ',
(i) T-peel peel force at a peel rate of 1000 mm / min after 110 ° C. treatment (T-peel peel force at a peel rate of 1000 mm / min in (d) above) is expressed as P _B ′,
(j) T-peel peeling force at a peeling speed of 10000 mm / min after treatment at 110 ° C. (T-peel peeling force at a peeling speed of 10,000 mm / min in the above (d)) is expressed as P _C ′,
When _a, P B / _{P A values,} P C / _{P A} value, _{P A} '/ _{P A} values, _{P B'} / _{P B} value, in Table 1 together results in _{P C} '/ _{P C} value Show.
In addition, the thickness of the outermost layer of Example 1 is 0.5 μm, the thickness of the intermediate layer is 0.2 μm, the haze degree of Example 1 is 4.3, the protruding ridge height Rpk is 0.025 μm, and the surface strength. (1) 31B evaluation was (circle) and surface strength (2) 31D evaluation was (circle).

As shown in Table 1, in the peelable (for peeling) film of Example 1, the specific gravity of the resin component that is the main component of the outermost layer is 1.15 g · cm ⁻³ or less, and the resin component The glass transition temperature is -10 to 75 ° C. for that reason,
(1) Each peeling force when the heat treatment temperature is 23 ° C. and 110 ° C. shows a finite value (exceeds 0) and shows a low value. Therefore, the film of the present invention including the film of Example 1 can be used effectively for peeling. Also,
(2) Accelerated peeling change rates P _B / P _A and P _C / P _A are the above desired values. Therefore, the film of the present invention including the film of Example 1 is useful as a peelable (peelable) film, and particularly useful as a peelable (peelable) film for high-speed peeling. Also,
_{(3) P A '/ P} A values, _{P B'} showing the peel force heat treatment temperature dependence / _{P B} value, _{P C} '/ _{P C} value is above the desired value, respectively. Therefore, the peeling force of the film of Example 1 is stable regardless of the heat treatment temperature. Therefore, the film of the present invention including the film of Example 1 is particularly useful as a peelable (peelable) film that is stable with respect to temperature without depending on the temperature environment.

Claims (10)

At least, a base material layer and an outermost layer are laminated in order , and a peelable film in which an intermediate layer is formed between the base material layer and the outermost layer ,
The outermost layer contains a resin component as a main component,
The resin component has a specific gravity of 1.15 g · cm ⁻³ or less,
The glass transition temperature of the resin component Ri -10～75 ° C. der,
The intermediate layer contains a polyolefin obtained by graft copolymerization with a hydroxyl group-containing (meth) acrylic acid ester and / or a hydroxyl group-containing vinyl ether.
A peelable film characterized by that. The peelable film according to claim 1, wherein the resin component contained as a main component of the outermost layer includes a structural unit derived from 4-methylpentene-1. Wherein the resin component contained as the outermost layer of the main component comprises a 4-methylpentene-1 polymer A, peelable film according to claim 1 or 2. The resin component contained as a main component of the outermost layer includes (1) a 4-methylpentene-1 polymer A and (2) an olefin resin A ′ other than the 4-methylpentene-1 polymer A. The peelable film according to any one of claims 1 to 3 , further comprising: The peelable film according to any one of claims 1 to 4 , wherein a T-peel peeling force (1000 mm / min) to the polyester adhesive tape on the film surface on the outermost layer side is 0.1 to 1.0 N / 25 mm. . The said polymer A is a peelable film of Claim 3 or 4 which has melting | fusing point of the range of 80 to 240 degreeC. The outermost layer has a thickness of 0.1 to 3.0 m, the peelable film according to any one of claims 1-6. The peelable film according to any one of claims 1 to 7 , wherein the intermediate layer has a thickness of 0.04 to 1.5 µm. The peelable film height according to any one of claims 1 to 8 , wherein a protruding peak height (Rpk) in a load curve obtained from a roughness curve of the film surface on the outermost layer side is 0.005 to 0.04 µm. . The peelable film according to any one of claims 1 to 9 , wherein the peelable film is used for applications having a peel rate of 1000 m / min or more.

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